Liquid dishwashing detergent composition for improved hand washing of dishes in cold water

ABSTRACT

A liquid dishwashing detergent composition for hand washing of dishes in cold water includes a synthetic organic nonionic detergent, a cationic surface active agent, a water soluble C 21  dicarboxylic salt and an aqueous medium. The proportion of the combination of nonionic detergent and cationic surface active agent is a detersive proportion, useful to remove fatty deposits on dishes, and the proportion of the C 21  dicarboxylic salt is sufficient to improve the detersive action in cold water of the combination of nonionic detergent and cationic surfactant so that the composition better removes fatty deposits on dishes being washed. Preferably, the liquid dishwashing detergent composition comprises 10 to 20% of a nonionic detergent, which is a condensation product of 3 to 20 moles of ethylene oxide with one mole of higher fatty alcohol of 10 to 16 carbon atoms per mole, 10 to 20% of ##STR1## wherein R is a hydrocarbyl chain of 8 to 22 carbon atoms and X is a halogen selected from the group consisting of chlorine and bromine, 1 to 5% of a salt of C 21  dicarboxylic acid, selected from the group consisting of sodium, potassium, ammonium and triethanolamine salts, and mixtures thereof, and 50 to 80% of water.

This invention relates to detergent compositions. More particularly, itrelates to a liquid dishwashing detergent composition, useful for handwashing (as distinguished from machine washing) of dishes in cold water,and for effectively removing fatty deposits from such dishes despite thefact that the dishwater is at a temperature lower than that which isusually considered to be necessary for effective removal of fattymaterials from the dishes.

Dishwashing detergents, useful for hand dishwashing (and not irritatingto the hands), have been invented and have been perfected so that smallproportions thereof are sufficient to wash ordinary dirty dishesefficiently. Adjuvants, such as lower alkanolamides and amine oxides,have been employed in such compositions to improve foaming activity anddetergency. Yet, despite the fact that such liquid dishwashingcompositions had been found to be effective in hot water, they have beenfound to be unsatisfactory for cold water dishwashing. Especiallydifficult is the cold water washing of dishes on which there aredeposits of normally solid fatty materials, such as hamburger grease andbeef fat. Consequently, the present invention, which allows effectivecold water washing of dishes containing deposits of such solid fats,represents a significant breakthrough in detergent research.

The prior art discloses a synergistic detergency of nonionic andcationic surface active agents, especially when used for the washing oflaundry, which is to be effected at room temperature or lower. Suchsynergism is described in an article by Rubingh et al. in 1982 Ind. Eng.Chem. Prod. Res. Dev. No. 21, at pages 176-182. U.S. Pat. Nos. 4,222,905and 4,259,217 describe heavy duty detergent compositions comprisingnonionic and cationic surfactants and mention that the detergentcompositions thereof are unusually effective in removing greasy and oilysoils, including body soil, from fabrics, and are also effective inremoving particulate soils. C₂₁ dicarboxylic acid, which is availablefrom Westvaco Corporation as DIACID® 1550, has been described aspossessing hydrotropic properties,and was said to have been used as itssoluble salts in certain detergents for its hydrotropic or solubilizingeffect on them, which detergents would otherwise have been less solublethan required. In articles entitled Industrial Utilization of C₂₁Dicarboxylic Acid, published at Vol. 52, J.A.O.C.S. 219-224 (1975), andHydrotropic Function of a Fatty Dicarboxylic Acid, at 20 TensideDetergents, No. 4 (1983), 177-180, the solubilizing effect of C₂₁dicarboxylic acid salts is mentioned. In those articles it was reportedthat such C₂₁ diacid salts are unique in the degree of water solubilitythey possess, and that they are capable of assisting in greatlysolubilizing other substances into aqueous systems in which suchsubstances are normally quite insoluble. The same articles mention thatthe C₂₁ dicarboxylic salts supplement the activity of the othersubstance so that less is required to achieve the desired results. U.S.Pat. No. 3,965,161 teaches usin C₂₁ dicarboxylic acid salts ashydrotropes or solubilizing agents in combination with nonionics to formbiodegradable and non-toxic cleaning compositions.

The prior art teaches that the presence of cationic surfactant withnonionic detergent synergistically improves the detergency of thenonionic, and that C₂₁ dicarboxylic salt can act as a hydrotrope and asa solubilizing agent for various materials, including nonionic surfaceactive agents. Applicant does not believe that C₂₁ dicarboxylic saltacts as a hydrotrope in the systems of this invention. Applicant hasfound that when C₂₁ dicarboxylic salt is added to a nonionic detergent,without any cationic surfactant being present, it does not increase thedetergency of the nonionic, and when too much dicarboxylic salt is addedto cationic and nonionic mixtures of detergents cleaning action isreduced. One who knew such facts would have found it surprising thatwhen the C₂₁ dicarboxylic salt is added to a detersive mixture ofnonionic detergent and cationic surface active agents, and the C₂₁dicarboxylic salt concentration is kept relatively low, significantimprovement in detergency is obtainable, especially for the removal offatty deposits from hard surfaces at low wash water temperatures.Accordingly, the present invention is unobvious from the prior art andfrom knowledge of the lack of favorable effect of the C₂₁ dicarboxylicsalt on the nonionic detergent. Additionally, when too much C₂₁ diacidsalt is present, e.g., as much C₂₁ diacid salt as detergent(nonionic+cationic), fat removal and other cleaning activities may bedecreased.

In accordance with the present invention a liquid dishwashing detergentcomposition for hand washing of dishes in cold water comprises asynthetic organic nonionic detergent, a cationic surface active agent, awater soluble C₂₁ dicarboxylic salt and an aqueous medium, withproportions of the first three such components being such that that ofthe combination of nonionic detergent and cationic surface active agentis a detersive proportion for fatty deposits on dishes and that of theC₂₁ dicarboxylic salt is sufficient to improve the detersive action incold water of the combination of nonionic detergent and cationicsurfactant with respect to fatty deposits on dishes being washed.Preferred liquid dishwashing detergent compositions comprise 10 to 20%of nonionic detergent, which is a condensation product of 3 to 20 molesof ethylene oxide with one mole of higher fatty alcohol of 11 to 16carbon atoms per mole, 10 to 20% of ##STR2## wherein R is a hydrocarbylchain of 8 to 22 carbon atoms, and X is a halogen selected from thegroup consisting of chlorine and bromine, 1 to 5% of salt of C₂₁ diacid,selected from the group consisting of sodium, potassium, ammonium andtriethanolamine salts, and mixtures thereof, and 50 to 80% of water.Also within the invention is a process for washing dishes (and alsocooking utensils)in dishwater in which there is preferably present0.05.to 0.5% of synthetic organic nonionic detergent, 0.05 to 0.5 ofcationic surface active agent, and 0.005 to 0.05% of a water soluble C₂₁dicarboxylic salt, with the nonionic detergent and cationic surfaceactive agent being present in a combined proportion which is detersivefor fatty deposits on dishes, and the C₂₁ dicarboxylic salt beingpresent in a proportion sufficient to improve the detersive action incold water of the combination of nonionic detergent and cationicsurfactant with respect to fatty deposits on dishes being washed.

The nonionic detergents employed in the practice of this invention arecondensation products of lower alkylene oxide with hydroxy-containinglipophiles. Normally, the lower alkylene oxide will be ethylene oxideand the detergents will be made by condensation of ethylene oxide with alipophile-containing compound, such as a higher fatty or linear alcoholof 10 to 18, preferably 10 to 16, and more preferably 10 to 13, e.g.,10, 12, carbon atoms content (average). However, suitable mixtures ofethylene oxide and propylene oxide, sometimes with some butylene oxide,may also be employed as the hydrophile donors. Instead of the higheralcohol, higher alkyl-substituted phenols may be employed, such as thosewherein the alkyl is linear and of 7 to 9 carbon atoms. Block copolymersof ethylene oxide (hydrophilic) with propylene oxide and/or butyleneoxide (lipophilic) may also be utilized, such as those sold under thetrademark Pluronic®, e.g., Pluronics F-68 and L-44. When the nonionicdetergent is a condensation product of ethylene oxide and higher fattyalcohl or alkyl phenol there will normally be from 3 to 20 moles ofethylene oxide per mole of nonionic detergent product. Preferably suchrange will be from 4 to 20 and most preferably from 4 to 15, e.g., 4, 6,9, 11 or 12. Of course, the number of moles of lower alkylene oxide permole of detergent is an average because such detergents are made asmixtures.

The cationic surface active agent utilized in the present invention ispreferably a quaternary ammonium halide, although analogous phosphoniumcompounds may be employed under certain circumstances. Variousquaternary ammonium halides may be utilized but those which are mostsatisfactory are those which contain a higher alkyl substituent,preferably accompanied by a plurality of lower alkyl substituents. Thus,it may be of the formula ##STR3## wherein R is a hydrocarbyl chain from8 to 22 carbon atoms and X is a halogen selected from the groupconsisting of chlorine and bromine. The higher alkyl, which may be of 10to 18 carbon atoms, is preferably a single higher alkyl, and three loweralkyls, of 1 to 3 carbon atoms, are also present. Still, in somecircumstances one of such lower alkyls may be replaced by another higheralkyl or another lipophilic groups, and sometimes such group may includea plurality of ethoxy groups in a chain. Preferred higher alkyls arethose of 12 to 16 carbon atoms, and the preferred lower alkyl is methyl.While all halogens may be used to make quaternary ammonium halides,normally employment of the fluoride and iodide will be avoided and thechlorides and bromides will be most effective. The following arerepresentative of some of the preferred quaternary ammonium halidesemployed: myristyl trimethylammonium bromide, lauryl trimethylammoniumbromide, cetyl trimethylammonium bromide, myristyl trimethylammoniumchloride, lauryl trimethylammonium chloride and cetyl trimethylammoniumchloride. Dimyristyl dimethylammonium bromide and the correspondingchloride are also operative but preferably the correspondingtrimethylammonium derivatives will be used instead.

The C₂₁ dicarboxylic acid, which is usually employed in the form of itsalkali metal, ammonium or lower (2 to 3 carbon atoms alkyl) alkanolaminesalt, preferably a di-salt of sodium, potassium, ammonia ortriethanolamine, is a cycloaliphatic dicarboxylic acid of the structure:##STR4## wherein x and y are integers from 3 to 9, x and y togetherequal 12, and wherein one Z is hydrogen and the other is a carboxylicacid group. The isomers wherein x is 5 and y is 7 form a preponderanceof the acid composition but there are also present minor amounts of theC₂₁ dicarboxylic acid wherein the cyclohexene ring varies in positionalong the carbon chain, and minor amounts of dicarboxylic acids of othermolecular weights. Typically, the C₂₁ dicarboxylic acid is of amolecular weight of 352.5, a saponification number of 312, a refractiveindex at 25° C. of 1.485, and a density at 25° C. of 1.024 g./ml. TheC₂₁ dicarboxylic acid, the salts thereof, the physical characteristicsthereof and methods for manufacturing it are described in U.S. Pat. No.3,956,161, which is hereby incorporated by reference. The C₂₁dicarboxylic salts are made by neutralizing the C₂₁ dicarboxylic acidwith a suitable neutralizing agent, such as ammonia, triethanolamine,diethanolamine, sodium hydroxide or potassium carbonate, and theproducts of such neutralization may be the corresponding mono- and/ordi-salts. Of these, it is considered that the di-salts are best in thepresent compositions and processes, but in some cases the mono-salts areoperative too, and mixtures are also useful.

The final required component of the present compositions is an aqueousmedium. Such medium will comprise water, preferably as a major componentthereof, and may also include other liquid solvents, such as: loweralcohols, e.g., ethanol; lower glycols, e.g., ethylene glycol, propyleneglycol; and lower alkyl ethers of lower glycols, e.g., Cellosolves. Suchco-solvents, in addition to helping to solubilize various components ofthe liquid detergent composition, and improving product homogeneity, mayalso serve as anti-freezes, preventing solidification of the detergentcomposition in cold weather.

The water in the present liquid detergents is preferably deionized waterbut other soft waters, and even tap waters, may be employed. However,usually it will be desirable to keep the water hardness below 150p.p.m., preferably below 100 p.p.m. and more preferably below 50 p.p.m.,as calcium carbonate. If ethanol is utilized it will normally bedenatured, e.g., SDA 40.

With the "active" and aqueous medium components mentioned above theremay also be included various other materials for improving physicalproperties of the liquid detergent and for producing special washingeffects. Such adjuvants include: thickeners, e.g., carrageenan; foamingagents, e.g., lauric myristic diethanolamide; opalescing and pearlescingagents; antibacterial materials, e.g., trichlorocarbanilide; colorants,such as dyes and pigments; antifoams, such as dimethyl silicone;enzymes, such as proteases and amylases; and perfumes. It may alsosometimes be desirable to include ionizable inorganic salts, which havebeen found useful to improve detergency of the present detergentcompositions. Sometimes the presence of such ionizable salts in thepresent liquid detergents can destabilize the detergent, and in suchinstances it will often be desirable to employ enzymes instead of suchbuilder salts to increase detergency. The enzyme or enzymes will bechosen to break down particular soils present on dishes, which arelargely fats, proteins and starches.

The proportions in the present detergent compositions of the nonionicdetergent, cationic surface active agent, C₂₁ dicarboxylic salt, andaqueous medium are usually from 5 to 25 parts of nonionic detergent, 5to 25 parts of cationic surface active agent, and 0.5 to 10 parts of C₂₁dicarboxylic salt, and preferably the ratio of nonionic detergent:cationic surface active agent (surfactant) will be in the range of 4:1to 1:2. For better detergency the C₂₁ dicarboxylic salt will be from 3to 15%, more preferably 5 to 12% of the sum of the non-ionic detergentand cationic surfactant. Although the percentages given are preferred,one may also make more dilute detergent compositions, and employ more ofthem in the dishpan. Thus, concentrations of the nonionic detergent andcationic surfactant as low as 0.5%, with the C₂₁ dicarboxylateconcentration at 0.1% have proven useful (especially when sodiumtripolyphosphate is present in a concentration of 2 to 10% (it helps toremove "dried on" fats). With such compositions concentrations of 5 to25% may be employed, and sponge application may be desirably practical.

The proportions given above will also set the proportions of the recitedcomponents in the wash water. Such wash water solution of detergentcomposition components is preferably made by dissolving the detergentcomposition in the water, but alternatively, such components may beadded to the water or the water may be added to them. In either case theresult is improved detergency with respect to the removal of fattydeposits from the dishes, especially when they are washed in dishwaterat room temperature or lower. Although the primary utility of thepresent liquid detergent compositions is in quickly and effectivelyremoving fatty deposits from hard surfaced substrates, using cold water,such improved detergency is also obtained with respect to oily, gummy,proteinaceous, starchy and sticky deposits and soils. Handwashing withcold dishwaters containing the components of the present compositionsquickly and effectively removes all the usual food residues from dishesand cooking utensils and the invented product is superior in thisrespect to commercial liquid hand dishwashing compositions, especiallyfor the removals of hamburger grease, beef fat, lard, butter, margarine,mayonnaise, and other fatty and oily foods. Another significantadvantage of the invention is the antibacterial action of the quaternarysalt, which is especially important for a product intended for coldwater washing. Additionally, the cationic component helps to prevent anybacterial growths from developing in the detergent composition duringlengthy storages in opened containers.

The liquid detergent compositions of this invention will preferablycomprise from 10 to 22% of nonionic detergent, 10 to 22% of cationicsurface active agent, 1 to 6% of water soluble C₂₁ dicarboxylic salt,and 50 to 80% of aqueous medium, often 70% thereof or more of water andsometimes entirely of water. Adjuvants for such compositions may make upany balances, to 100%. Usually the total proportion of adjuvant(s) willbe limited to 20% and often will be in the range of 1 to 10%. Individualadjuvants will usually be 0.1 to 5% of the composition, if present. Morepreferred percentages of the required components are 12 to 18, 12 to 18,2 to 4 and 60 to 75, respectively, with most preferred proportions beingabout 18%, 18%, 4% and 60%, respectively.

When dishes are washed with the invented compositions (or with thecomponents thereof in the described proportions) the concentration ofthe composition (or total of the components) in the dishwater isnormally in the range of 0.1 to 10%, preferably 0.3 to 3%, and morepreferably, for economy, about 0.5 to 1%, e.g., 0.8%. Suchconcentrations will often correspond approximately to 0.02 to 1.4%, 0.05to 0.5%, 0.07 to 0.2%, and 0.1%, respectively, for the nonionicdetergent and for the cationic surfactant, and 0.005 to 0.3%, 0.005 to0.05%, 0.01 to 0.03% and 0.02%, respectively, for the C₂₁ dicarboxylicsalt, in the dishwater. While the lower concentrations within the aboveranges are more frequently used, that is for economic reasons; the moreof the product that is employed, the better its performance. Thus,whereas when the liquid detergent is applied to a wet sponge and dishesare wiped with the sponge, concentrations of the detergent that are ashigh as 10% could be used, for normal dishpan or sink washing of dishesthe concentrations will be much lower and can be lower still when longsoaking periods are utilized, and when the food remains on the dishesare not difficult to remove (not hard fats). Normally, a combination ofsoaking and mechanical action will be found to be best for quick andeffective dishwashing.

The dishwater will preferably be relatively soft but the inventeddetergent compositions and the components thereof are capable ofeffectively washing dishes in hard waters, usually of mixed calcium andmagnesium hardness, although hardness is preferably in the 0 to 100 or150 p.p.m. range. Generally, the hotter (or warmer) the water the betterthe wash, because warmer water tends to melt and dissolve the deposits,such as fats and greases, better. The compositions of this invention arealso useful for hot water dishwashing but are especially useful for roomtemperature or cold water dishwashing because, without the need formelting the fatty or greasy materials on the dishes, the combination ofactive components of this invention significantly promotes the releaseof such deposits during washing in room temperature or cold dishwater.This action is attributable to a unique combination of "undermining" and"rolling up" actions of the composition, which loosens and removes thefat from the substrate, and an emulsification action, due to which thefat is moved away from the dishwater-dish interface. While higher watertemperatures up to boiling may be employed, if feasible, normaldishwashing temperatures will be in the range of 35° to 50° C. Thepresent detergent compositions (and the components thereof) result insatisfactory removal from dishes of usually very difficult to removefatty deposits and smears at lower temperatures, such as those in therange of 10° to 40° C. While cleaning is not as good in the lower partof this range as in the upper part, it is feasible to conduct thedishwashing at temperatures in the range of 10° to 20° C., with theresults obtainable being comparable to those obtained when washing athigher recommended temperatures with conventional commercial liquiddishwashing detergents intended for hand dishwashing. It is preferredthat the dishwater be at a temperature in the ranges of 20° to 35° C. or20° to 25° C., e.g., 30° C. and 23° C., for best "room temperature"dishwashing, in which significant improvements in fat removal areobtained, compared to control commercial detergent compositions.

The following examples illustrate but do not limit the invention. Allparts in the examples and in the specification and claims are by weight,and temperatures are in ° C., unless otherwise indicated.

EXAMPLE 1

    ______________________________________                                        Component        Percent                                                      ______________________________________                                        Nonionic detergent.sup.1                                                                       14.2                                                         Cationic surfactant.sup.2                                                                      14.2                                                         C.sub.21 dicarboxylate.sup.3                                                                   2.8                                                          Water, deionized 68.8                                                                          100.0                                                        ______________________________________                                         .sup.1 Neodol 236.5 (condensation product of 6.5 moles of ethylene oxide      with one mole of higher fatty alcohol averaging 12 to 13 carbon atoms)        .sup.2 Tallowalkyl trimethylammonium chloride                                 .sup.3 Ditriethanolamine salt of Diacid 1550 (Westvaco Corp.)            

Equal proportions of hamburger grease are smeared onto upper surfaces ofeach of four identical circular stainless steel planchets and theplanchets are each placed, coated side up, in identical differentbeakers containing different dishwaters in which there are present 1% ofdifferent dishwashing liquid compositions. The dishwashing liquidsemployed are three commercial liquid dishwashing detergent and theinvented liquid dishwashing composition of this example. The threecommercial products are Palmolive (beaker No. 1), Dawn (beaker No. 2)and Ajax (beaker No. 3), and the experimental composition is in beakerNo. 4. The dishwaters are at 25° C.

After soaking of the planchets for one hour the dishwaters are comparedfor cloudiness, which is indicative of the amount of hamburger greaseremoved from the planchets and suspended or emulsified in the dishwater.By visual comparison it is found that the water in beaker No. 4 isdefinitely cloudier than the waters in the other three beakers. Also,visual examination of the planchets indicates that more hamburger greasewas removed from the planchet in beaker No. 4.

Similar results are obtainable when the dishwater is at 20° C. and when,instead of hamburger grease, beef fat or lard is employed as the fattymaterial on the planchets.

When the experiment is repeated, with beef fat on ceramic plates,essentially the same results are obtained. Also, when instead of soakingfor one hour without the application of mechanical energy to the plates,the plates are soaked for five minutes and then lightly hand sponged,the "experimental" product is found to be superior to the commercialproducts in removing the beef fat at 20° C. and at 25° C., andessentially all of the fat is removed in such experiments when theexperimental product is employed. When the commercial products are usedthe plates are still greasy. Such results are also obtainable when theconcentration of the liquid detergents is 0.1%, 0.15% and 0.2%, when the5-minute soak, followed by light sponging, is employed, and in somecases, when only sponging or wiping with a sponge or cloth soaked indishwater is practiced.

Results like those described above are also obtainable when theexperimental product contains from 5 to 25% of nonionic detergent, 5 to25% of cationic surfactant, 0.5 to 5% of C₂₁ dicarboxylate, and 45 to89.5% of aqueous medium, of which at least half, or a major proportion,is water.

Also, when instead of the triethanolamine salt of the C₂₁ dicarboxylicacid, other salts thereof, such as the ammonium salt and the loweralkylamine salts, e.g., the mono-, di-, and tri-ethylamine salts orother such salts wherein the lower alkyl is of 1 to 3 carbon atoms areemployed, similar good results will be obtained. When the alkali metal(sodium and potassium) salts of the C₂₁ dicarboxylic acid are employedthe results are still good but not as favorable as with the ammonium andtriethanolamine salts.

In some experiments that have been run soaking tests at concentrationsof liquid dishwashing detergent composition above those normallyemployed have been employed. Use of the soaking test avoids anyvariations in the applications of mechanical energy to the surfacesbeing cleaned and it has been found that the soaking test results aresimilar, relatively, to actual use tests. The employment of higherconcentrations of the liquid dishwashing detergent compositions allowsobtaining results in less time, and the results are relatively the sameas those for actual use tests.

EXAMPLE 2

    ______________________________________                                        Component              Percent                                                ______________________________________                                        Igepal ® CA-630.sup.4 (GAF Corporation)                                                          15.0                                                   Myristyl trimethylammonium bromide                                                                   8.0                                                    C.sub.21 dicarboxylate.sup.5                                                                         2.0                                                    Water, deionized       75.0                                                                          100.0                                                  ______________________________________                                         .sup.4 Octyl phenoxypoly(ethyleneoxy) ethanol                                 .sup.5 Ammonium salt of Diacid 1550, made by ammonium hydroxide               neutralization of Diacid 1550, which had been obtained from Westvaco Corp                                                                              

The liquid detergent is clear and stable on storage at elevatedtemperature.

When the experiments of Example 1 are repeated, using this liquiddishwashing detergent composition, essentially the same results areobtained. When the temperature of the dishwater is raised to 50° C. theexperimental composition and the three commercial liquid detergentcompositions, mentioned in Example 1, all satisfactorily clean thesubstrates of the fatty deposits, in both the sponging and soakingtests.

The soaking test results are verified by utilizing scales, which measurethe losses in weights of the planchets and dishes during the soakingtest, due to removals therefrom of the fatty deposits, caused by actionsof the liquid detergent compositions in the dishwaters.

EXAMPLE 3

    ______________________________________                                        Component        Percent                                                      ______________________________________                                        Chemal ® DA-4.sup.6                                                                        18.0                                                         Adogen ® 471.sup.7                                                                         18.0                                                         C.sub.21 dicarboxylate.sup.3                                                                   3.6                                                          Water            60.4                                                                          100.0                                                        ______________________________________                                         .sup.6 Condensation product of four moles of ethylene oxide with one mole     of higher fatty alcohol of 10 carbon atoms                                    .sup.7 Octadecyl trimethyl ammonium bromide                                   .sup.3 Ditriethanolamine salt of Diacid 1550 (Westvaco Corp.)            

A clear liquid dishwashing detergent composition of the above formula ismade by admixing the components thereof. Then, three grams of suchcomposition are dissolved in water to make 100 milliliters of dishwaterat 25° C. Control dishwaters containing equivalent proportions ofcommercial dishwashing detergents sold under the trademarks DAWN(Procter & Gamble) and PALMOLIVE (Colgate-Palmolive Company) are made,with the proportions employed being such that the active ingredientcontents (organic detergents and surfactants) are the same. Three wirescreen squares are prepared with equal weights of lard smeared onto themand they are simultaneously suspended in the dishwaters. The beakercontaining the dishwater made with the dishwashing detergent compositionof this invention immediately turns cloudy and an observer can note avigorous action at the lardsolution interface as the lard is beingremoved from the wire screen and is being emulsified into the dishwater.On the other hand, the control compositions apparently do notsignificantly remove the lard from the wire screen and there are littleor no observable changes in the control dishwaters. The reported testhas been shown by other experiments to indicate the relative dishwashingeffectiveness of dishwashing compositions, with respect to removal offatty soils from hard surfaces.

EXAMPLE 4

    ______________________________________                                        Component              Percent                                                ______________________________________                                        Neodol 23-6.5          1.0                                                    Myristyl trimethyl ammonium bromide                                                                  1.0                                                    Ammonium C.sub.21 dicarboxylate                                                                      0.2                                                    Sodium tripolyphosphate                                                                              4.0                                                    Water, deionized       93.8                                                                          100.0                                                  ______________________________________                                    

A liquid detergent composition of the above formula is made bydissolving the indicated components in the water to produce a clearproduct. When such product is employed at a concentration of about 10%in dishwater and is sponged onto dishes containing "dried-on" depositswhich have been standing overnight, the deposits are readily removeddespite the fact that the dishwater is at a temperature as low as 20° C.Normally, for environmental reasons, phosphates will be omitted from thedishwashing compositions of the present invention but it has been foundthat they help to remove dried on and hardened deposits of fattymaterials from dishes and cooking utensils, and accordingly, they may beincorporated in compositions intended for such uses. Also, they do notadversely affect hand dishwashing of dishes and utensils soiled withnormal fatty deposits.

EXAMPLE 5

When the proportions of components of the formulas given in Examples 1-4are varied ±10% and ±25%, while remaining within the ranges set forth inthe specification, essentially the same superiority for the compositionsof the invention, compared to the commercial products, will be obtainedat temperatures from 10° C. up to 35° or 40° C., with the differencesbeing greater at the lower temperatures. Often the concentrations of thepresent detergent compositions in the dishwater will be at least 0.1%,preferably at least 0.2%, and more preferably at least 0.5% for bestdetergency but lesser proportions can be used effectively and greaterproportions result in better fatty soil removals.

The invention has been described with respect to illustrations andworking embodiments thereof but is not to be limited to these because itis evident that one of skill in the art, with the present specificationbefore him, will be able to utilize substitutes and equivalents withoutdeparting from the invention.

What is claimed is:
 1. A liquid dishwashing detergent composition, forhand washing of dishes in cold water, which comprises, by weight, 5 to25 parts of synthetic organic nonionic detergent, 5 to 25 parts ofcationic quaternary ammonium halide surface active agent, 0.5 to 10parts of a water soluble C₂₁ diarboxylic salt and 40 to 100 parts ofaqueous medium, with the proportions of the synthetic organic nonionicdetergent, the cationic surface active agent and the C₂₁ dicarboxylicsalt being such that the proportion of the combination of such nonionicdetergent and cationic surface active agent is a detersive proportion,useful for the removal of fatty deposits from dishes, and the proportionof the C₂₁ dicarboxylic salt is sufficient to improve the detersiveaction in cold water of the combination of nonionic detergent andcationic surface active agent with respect to such fatty deposits ondishes being washed, and with the proviso that the weight of the C₂₁dicarboxylic salt is in the range of 5 to 12% of the sum of the weightsof the nonionic detergent and cationic surface active agent.
 2. A liquiddishwashing detergent composition according to claim 1 wherein thenonionic detergent is a condensation product of a lower alkylene oxideand a higher fatty alcohol or phenol, the cationic surface active agentis a quaternary ammonium halide, the dicarboxylic salt is a salt of acation selected from the group consisting of sodium, potassium,ammonium, lower alkylamine, and lower alkanolamine, and the aqueousmedium includes a major proportion thereof of water.
 3. A liquiddishwashing detergent composition according to claim 1 wherein theweight ratio of nonionic detergent to cationic surface active agent isin the range of 1:2 to 4:1.
 4. A liquid dishwashing detergentcomposition for hand washing of dishes in cold water, which comprises,by weight, 10 to 20% of nonionic detergent, which is a condensationproduct of 3 to 20 moles of ethylene oxide with one mole of higher fattyalcohol of 10 to 16 carbon atoms per mole, 10 to 20% of ##STR5## whereinR is a hydrocarbyl chain of 8 to 22 carbon atoms, and X is a halogenselected from the group consisting of chlorine and bromine, 1 to 5% ofsalt of C₂₁ diacid, selected from the group consisting of sodium,potassium, ammonium and triethanolamine salts, and mixtures thereof, and50 to 80% of water, with the proviso that the weight of the salt of C₂₁diacid being in the range of 5 to 12% of the sum of the weights of thenonionic detergent and ##STR6##
 5. A liquid dishwashing detergentcomposition according to claim 4 which comprises by weight about 18% ofnonionic detergent which is a condensation product of 4 to 7 moles ofethylene oxide and a mole of higher fatty alcohol of 10 to 13 carbonatoms, about 18% of tallowalkyl trimethyl ammonium chloride, about 4% oftriethanolamine salt of C₂₁ diacid and about 60% of water.
 6. A processfor washing dishes to remove fatty deposits from the surfaces thereofwhich comprises washing said dishes in dishwater in which there ispresent, by weight, 0.05 to 0.5% of synthetic organic nonionicdetergent, 0.05 to 0.5% of cationic quaternary ammonium halide surfaceactive agent, and 0.005 to 0.05% of water soluble C₂₁ dicarboxylic salt,with the proviso that the nonionic detergent and cationic surface activeagent being present in a combined proportion which is detersive forfatty deposits on dishes, and the C₂₁ dicarboxylic salt being present ina proportion, from 5 to 12%, by weight, of the combined proportion ofnonionic detergent and cationic surfactant, which is sufficient toimprove the detersive action in cold water of the combination ofnonionic detergent and cationic surfactant with respect to fattydeposits on dishes being washed.
 7. A process for washing dishesaccording to claim 6 wherein the weight ratio of nonionic detergent tocationic surface active agent is in the range of 1:2 to 4:1, thedishwater is at about room temperature and the dishes are hand washed toremove fatty deposits from the surfaces thereof.
 8. A process accordingto claim 6 which comprises washing said dishes in dishwater at atemperature in the range of 10° to 40° C., in which dishwater there ispresent, at a concentration of at least 0.1%, by weight, a detergentcomposition which comprises, by weight, 5 to 25 parts of syntheticorganic nonionic detergent, 5 to 25 parts of cationic surface activeagent, 0.5 to 10 parts of a water soluble C₂₁ dicarboxylic salt and 40to 100 parts of aqueous medium, with the proportions of the syntheticnonionic detergent, the cationic surface active agent and the C₂₁dicarboxylic salt being such that the proportion of the combination ofnonionic detergent and cationic surface active agent is a detersiveproportion, useful for the removal of fatty deposits from dishes, andthe proportion of the C₂₁ dicarboxylic salt is sufficient to improve thedetersive action in cold water of the Combination of nonionic detergentand cationic surface active agent with respect to such fatty deposits ondishes being washed, and with the proviso that the proportion of the C₂₁dicarboxylic salt is in the range of 5 to 12% of the sum of the weightsof the nonionic detergent and cationic surface active agent.
 9. Aprocess according to claim 8 which comprises washing said dishes indishwater at a temperature in the range of 20° to 35° C., in whichdishwater there is present at a concentration of at least 0.2%, byweight, a detergent composition which comprises, by weight, 10 to 20% ofnonionic detergent, which is a condensation product of 3 to 20 moles ofethylene oxide with one mole of higher fatty alcohol of 10 to 16 carbonatoms per mole, 10 to 20% of ##STR7## wherein R is a hydrocarbyl chainof 8 to 22 carbon atoms, and X is a halogen selected from the groupconsisting of chlorine and bromine, 1 to 5% of salt of C₂₁ diacid,selected from the group consisting of sodium, potassium, ammonium andtriethanolamine salts of such C₂₁ diacid, and mixtures thereof, and 50to 80% of water, with the weight proportion of the salt of C₂₁ diacidbeing in the range of 5 to 12% of the sum of the weights of the nonionicdetergent and ##STR8##
 10. A process according to claim 9 whichcomprises hand washing said dishes in dishwater at about roomtemperature, 20° to 25 C., in which dishwater there is present at aconcentration of at least 0.5%, by weight, a detergent composition whichcomprises, by weight, about 18% of nonionic detergent which is acondensation product of 4 to 7 moles of ethylene oxide and a mole ofhigher fatty alcohol of 10 to 3 carbon atoms, about 18% of tallowalkyltrimethyl ammonium chloride, about 4% of triethanolamine salt of C₂₁diacid and about 60% of water.